New phosphoric esters



NEW PHosrnoRIc ESTERS Jean Metivier, Arpajon, France, assignor toSociete des Usines Chimiqnes Rhone-'Poulenc, Paris, France, acorporation of France No Drawing. Filed Oct. 9, 1959, Ser. No. 845,318

Claims priority, application France Nov. 7, 1958 12 Claims. (Cl. 167-22)This invention relates to phosphoric esters, to a process for theirpreparation and to pesticidal compositions containing them.

The present invention provides new phosphoric esters of the generalformula:

wherein R represents a lower alkyl group, X, and X are the same ordifferent and represent oxygen or sulphur atoms, and R R R and R are thesame or different and represent hydrogen atoms or lower alkyl groups.

The term lower alkyl group is used herein to denote alkyl groupscontaining from 1 to 4 carbon atoms.

According to a feature of the invention these esters are prepared bycondensing a salt of a phosphoric acid of the general formula:

u i (RO)2PX2H II with a compound of the general formula:

R: Y-CH:-C=(|3--CON\ 1 R2 RA III (wherein Y represents a reactive esterresidue such as a halogen atom or a sulphuric or sulphonic ester residueand R, X X R R R and R, are as hereinbefore defined).

The phosphorus derivative of Formula H is preferably employed in theform of an alkali metal salt, which may if desired be prepared in situ,an ammonium salt or a salt with a tertiary organic base, for examplepyridine.

The reaction is preferably carried out in an organic solvent medium andmore particularly in an alcohol such as ethanol, a ketone such asacetone or methyl ethyl ketone, an ester such as ethyl acetate, anitrile such as acetonitrile, or an aromatic hydrocarbon such as benzeneor toluene, and at a temperature between room temperature and 120 C.

- When X and X in Formula. II represent a sulphur atom and an oxygenatom respectively (the thiolo form),-

there is obtained by this method an ester of Formula I wherein X and Xrepresent an oxygen atom and a sulphur atom respectively (the thioloform). This transposition is quantitative.

The new phosphoric esters of the invention exhibit outstandingpesticidal properties, particularly as insecticides and acaricides.

The present invention also relates to pesticidal compositions containinga phosphoric ester of general Formula I' in association with one or morediluents compatible therewith. The compositions may be solid if acompatible powdered solid diluent is used such as talc, mag nesia,kieselguhr, tricalcium phosphate, cork powder, absorbent charcoal or aclay such as kaolin or bentonite,

the quantity of phosphoric ester being preferably between 0.005 and 50%by weight of the compositions. In place of a solid there may be used aliquid in which the phosphorus derivative is dissolved or dispersed, itscontent being preferably between 0.005 and 50% by weight of thecomposition. The composition may thus be in the form of an aerosol, asuspension, an emulsion or a solution in an organic or aqueous-organicmedium, for example -an aromatic hydrocarbon, such as toluene or xylene,a mineral or vegetable oil or a mixture of these diluents. Compositionsin the form of dispersions, solutions or emulsions may contain ionic ornon-ionic wetting, dispersing or emulsifying agents, for examplesulphoricinoleates, quaternary ammonium derivatives or products based oncondensates with ethylene oxide, such as condensates of ethylene oxidewith octylphenol or fatty acid esters of anhydrosorbitols which havebeen solubilised by etherification of the free hydroxy groups bycondensation with ethylene oxide. It is preferable to use non-ionicagents because they are insensitive to electrolytes. When emulsions arerequired the phosphorus derivatives may be used in the form ofself-emulsifying concentrates containing the active substance dissolvedin the dispersing agent or in a solvent compatible with the said agent,a simple addition of water providing compositions ready for use.

The solid compositions are preferably prepared by grinding thephosphorus derivative with the solid diluent or by impregnation of thesolid diluent with a solution of the phosphorus derivative in a volatilesolvent, followed by evaporation of the solvent and, if necessary,grinding the product to obtain a powder.

These new compounds may be used in admixture with other pesticides,including substances producing a synergistic effect.

The following examples illustrate the invention.

Example I To a suspension of sulphur (7.2 g.) in a mixture ofdiethylphosphite (34.5 g.) in ethanol cc.) is added gradually a solutioncc.) of 2.5 N sodium ethoxide in ethanol.

After the reaction mixture has stood for one hour at room temperature,4-chlorocrotonamide (23.9 g.) is added and the mixture is heated for 6hours under reflux. After removal by filtration of the sodium chlorideformed the ethanol is distilled off under reduced pressure. The oilyresidue obtained (59 g.) is treated with distilled water (150 cc.).After treatment with decolourising charcoal and filtration, the aqueoussolution is extracted with chloroform (3 x cc.). The combined chloroformextracts are dried over sodium sulphate and concentrated under reducedpressure until no more solvent remains. The residue obtained weighs 41g. and analysis shows that it is4-0,0-diethylthiolophosphorylcrotonamide.

Example II To a solution of potassium 0,0-diethyldithiophosphate (17.9g.) in acetone (60 cc.) is added 4-chlorocroton amide (9 g.) and themixture is agitated for two hours at room temperature and then heatedfor one hour under reflux. The potassium chloride formed is removed byfiltration and the acetone solution is concentrated under reducedpressure. The oil obtained is dissolved inbenzene cc.) and the solutionobtained is washed with distilled water (50 cc.), with a saturatedsolution of sodium bicarbonate (50 cc.) and finally again with distilledwater (4 x 50 cc.). After drying over sodium sulphate and treating withdecolourising charcoal, concentration under reduced pressure until thesolvent hasdisappeared yields a viscous oil (15.2 g.) which analysisshows-tobe4-O;Odiethyldithiophosphorylcrotonamide;'

The 4-chlorocrotonamide which serves as starting material in Example Iand I1 is prepared by the method of Iiesp ieam Bul FSo c @him.,133f466{("19t) 59.; 71 'Y Example 111:

o.resolut on.. f. .p0t ssium 0,0- ie hy di hiophosp at (3 a) u ue.(140cm) s a ded N,N diethy -.4:- chlorocrotonamide (23.. gr). 'AfterB,hours agitation'at, room temperature and 1 hours heating under-reflux,the, mix ure is. treated. s-i11.. Examp1e.Il and n. oily produ (3.7 a) so tained, which. analysis shows. to;v e. Nildiethy1=4-Q,O=die hyldihiopho phoryl mtonamide.

ILN-d ethylf h orbcrotonam e which e es) s. rt ng. m r al is Prepare y:t e. ction. of loro crotonyl chloride; upon. diethylamine. It.dist-tiles at. 1Q6+1Q7 C 1.5 ,mm...Hg,.

Example V To a solution of potassium QQ-diethyldithiophosphate (26.4 g.)in acetone (120'- ce-. )'is-added N,N-dimethyl-4- hl r cro onamide' 6-g=-)- After 12 hoursy andinga r om t mp ure. he mixt re is. treatedasindic t d; in... xampl I1 and moilypro uct-(Z g l-i bt inedwhiehranalysis shows to be N,N-dimethyl4-0,0*diethyldithio ph sphorylerotonmide.

he ,N- ime hyl tcbloro roton mi e h h. r s -s rt n m ri ls warmed byhecti uo :diinethy1.-.- mine upper hlor rot uy chloride. .It. is. eaquid'; hoilingathlr r l Examp e. Ill

To: arsolutiorroft; potassium. Q50adiethyldithiophosphate (23.3 g.) in:aeetone'.-(.=1il0;cc.)- is added"N isopropyll-ivchlorocrotonamid'e.(l5;4. g:). After 12 hours standing at room.temperature followed by treatment as: in Ex. ample II,ayellowoiliis.obtained1 (26;5 g:), which analysis shows to beN-isopropyl-4-0,0?diethyldithiophosrphorylcrotonamide. a

The N-isopropyl-4-ehlorocrotonamide is prepared by the actiqaoimouoionropr amineupou. hloroerotony hloride, It is. a solid. inelfiagatfifiExampleila To, eetenitrileAJSfi .eez)sissaddecbN-methyhkchlome rotoemidelzfl'zgz) ndrammonium O,Q.-die.thylthioni1-@ phosphetei 35.32):..Qnd-lhflrinixtureis heateckfor =3'hoursx: 9.75;?- C.Aftererremoval bysfiltration v of the: am.-. mohiumc hLQride"; formemtfollowed; by: treatment. as; in. Elample 1:, an;.Qil-f(3i'.:.g. isiohtained; which. analysis:

shows to; be: N;inethyhAe0,0adiethylthiolophosphoryl crntpnamide Vasses.

Example VIII To acetonitrile (100 cc.) is added 98% ammonium:0,0-diethylthionophosphate (19.5 g.) and N,N-dimethyl-4-ehlorocrotonamide (13.5 g.). After 4 hours heating at 50-55 C.followed by treatment as in Example I,N,N-dimethyl-4-0,0-diethylthiolophosphorylcrotonamide (23 g.) is obas'ues zasazyellowoila m e -Examrzle l& *re aetesimre (rower addedammonium 0,0 diethylthionophosphate (25.5 g.) and N ethyl 4-eh1orolfislide .(;.1 4-. ):al .theufiatute s. eat d: at 5 C. for thours.

After -treatinent Example; 1;. Nethyl-4-O,'O-diethylthiolophosphorylcrgtonamide, 2,665. g.) is obtainedin the form of a yellow oil.

The N-ethyl-4-chlorocrotonamide which serves as starting mate ial igreparemby the .ac ipu of monoethy am n uppm4= hloro re nyl hl ride Aftr rec ys sat onx from water N-ethyl-4-chlorocrotonamide melts at 80Exampletx" To suspension of N-methyl-4-cliloroerotonamide (26.6' L

g.) in water-( 100 cc.) ammonium ogO-dimethylthionophosphate (38.4g.) isaddedand the-mixture is stirred for five hours at roomlemperature andthen heated for one hour to 80 C, Thesiolution obtained is extractedwith methylene chloride (4 x 100 cc.)', and" the extract is driediwith'sodium sulphate, treated with ,d'ecolor-ising charcoal and; evaporatedunder reduced pressure. A; viscous oil" (34 g.) remains; which analysisshows to'ibe N methyli t=OgOgdimethylthiolophosphorylcrotonamide.

Example XI To a solution of" N-methyl'-'4-OQ=diethylthiolophphorylcrotonamide (20 g.) in Xylene (25cc.)' isadd'ed 10 g. of acondensation product of 10 molecular proportions of ethylene oxideandonezmolecular proportion of octylphenol and themixture ismade up tocc. with xylene.

The solution obtained is diluted with water (100 litres). This aqueoussolution-sprayed upon apple trees infested with green aphids-leadstoithe total destruction of the latter.

- T01" a: solution; of: N-ethyl-4-0.q-diethylthiolophomphorylcrotonamide (10 g.) in acetone (20 cc.) is added: thewettingagent- (i-cm) describediimExampleXI.

Thesolutionnhtainediby dilution with;water;.(5.0 litres): is usedito.treat: Erench; Bean plantszinfesteel with-redipider;

ExamplaXIIl To. solu i n of. -0,0-diethy d hio h p lcr tonr.- amidet30:g.) in. xylene (50 g.) is added sodiumdioctyk suceinate sulp honatev(15 ,g andthe mixture is made .up to. 100 cc. with xylene,

The, solution obtained is dis; persed in water (100 litres).

The em lsion. h h arepared: m y: be ed gainst phids' nd redrsrziden. r

Lclai u; 1, Amemb eoi-the ela s ccmsistina-ip sthe ah snhhris. esiem' ith eneral t rraulee whereinKrepresents'a lower alkyl group, X andXi arechosen from the-group consisting of oxygen and sulphur, and R R2, R arechosen from thegroup con: sisting of hydrogen atoms andlower alkylgroups.

I 2. 4e0;Qdiethylthiolophosphorylerotonamide; 3i: 443,0diethyldithiophdsphorylcrotonamidet N-methyl 4 0,0diethyldithiophosphorylcroton 5f I -I,N-diethyl 4.0,0diethyldithiophosphorylcrotong ILN-dimethyl-4-O,O-diethyldithiophdsphorylcrotan- 7 1 I-isopropyl 4-0,0diethyldithiophosphorylcrotony?! methyl 40,0diethylthiolopliosphorylcroton 9i 1-I,N-dimethyl-4-O,O-tiiethylthiolophosphoifiylcrotoni i fi ethyl 40,0-diethylthiolophosphorylcroton- N-methy1-4-0,0dimethylthiolophosphorylcroton- A pesticidai composition comprising atleast one member of the class consisting of the phosphoric esters of thegeneral formula:

%1 (RO);PXzCHs(3= l3C O-N R1 R1 R4 wherein R represents a lower alkylgroup, X and X, are chosen from the group consisting of oxygen andsulphur, and R R R and R are chosen from the group consisting ofhydrogen atoms and lower alkyl groups in association with at least onediluent compatible therewith.

References Cited in the file of this patent UNITED STATES PATENTS2,802,855 Whetstone Aug. 13, 1957

1. A MEMBER OF THE CLASS CONSISTING OF THE PHOSPHORIC -ESTERS OF THEGENERAL FORMULA:
 12. A PESTICIDAL COMPOSITION COMPRISING AT LEAST ONEMEMBER OF THE CLASS CONSISTING OF THE PHOSPHORIC ESTERS OF THE GENERALFORMULA: